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Synthesis and Characterization of a Metalloid Ge 6 Cluster with Bulky Amide Ligands.

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Title: Synthesis and Characterization of a Metalloid Ge 6 Cluster with Bulky Amide Ligands.
Authors: Liu, Jingjing1,2 (AUTHOR), Liu, Xiaoting1,2 (AUTHOR), Zhang, Bin1,3 (AUTHOR), Ji, Caiting1 (AUTHOR), Sun, Xiaohui1,2 (AUTHOR), Wang, Wenyuan2,3 (AUTHOR) wangwy@nwu.edu.cn, Bo, Xiaoxu3 (AUTHOR) boxxsci@163.com
Source: Materials (1996-1944). Jun2026, Vol. 19 Issue 12, p2516. 12p.
Subjects: Metal clusters, Ligands (Chemistry), X-ray diffraction, Molecular structure, Germylenes, Electron delocalization
Abstract: This article details the synthesis and structural characterization of a new metalloid germanium cluster 3 with bulky amide ligands. The cluster features a Ge6 core stabilized by four -N(SitBuMe2)2 ligands and was obtained via reduction of the amido trichlorogermane 2 using potassium chips in toluene. Single-crystal X-ray diffraction analysis revealed that the Ge6 core adopts a butterfly-shaped geometry with a Ge-Ge dumbbell unit, which contains two unsubstituted germanium atoms exhibiting prominent lone-pair characteristics. The Ge6 core can also be classified as a nido cluster, with a cluster-bonding-electron count of 16, perfectly satisfying the 2n + 4 electron-counting rule. Combining the structural features of this nido cluster with the bond length distribution in the folded four-membered ring suggests that the Ge4 ring features a certain degree of electron delocalization. Additionally, two bis(amido)-substituted germylenes (4 and 6) were isolated and structurally characterized. They exhibit analogous structural features, with each germanium center adopting a two-coordinate V-shaped configuration, the Ge–N bond lengths being very similar, and the nitrogen atoms adopting a planar triangular geometry. Notably, compound 6, bearing bulkier -N(SiiPr3)2 substituents, exhibits a significantly larger N-Ge-N bond angle (120.58°) compared to the corresponding value of 113.54° observed for compound 4 with -N(SitBuMe2)2 substituents. This clearly demonstrates that the steric bulk of the substituents exerts a remarkable influence on the molecular geometry and σ-donor ability of the lone pairs on germanium centers. [ABSTRACT FROM AUTHOR]
Copyright of Materials (1996-1944) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Synthesis and Characterization of a Metalloid Ge 6 Cluster with Bulky Amide Ligands.
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  Data: <searchLink fieldCode="JN" term="%22Materials+%281996-1944%29%22">Materials (1996-1944)</searchLink>. Jun2026, Vol. 19 Issue 12, p2516. 12p.
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  Data: <searchLink fieldCode="DE" term="%22Metal+clusters%22">Metal clusters</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+diffraction%22">X-ray diffraction</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Germylenes%22">Germylenes</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+delocalization%22">Electron delocalization</searchLink>
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  Data: This article details the synthesis and structural characterization of a new metalloid germanium cluster 3 with bulky amide ligands. The cluster features a Ge6 core stabilized by four -N(SitBuMe2)2 ligands and was obtained via reduction of the amido trichlorogermane 2 using potassium chips in toluene. Single-crystal X-ray diffraction analysis revealed that the Ge6 core adopts a butterfly-shaped geometry with a Ge-Ge dumbbell unit, which contains two unsubstituted germanium atoms exhibiting prominent lone-pair characteristics. The Ge6 core can also be classified as a nido cluster, with a cluster-bonding-electron count of 16, perfectly satisfying the 2n + 4 electron-counting rule. Combining the structural features of this nido cluster with the bond length distribution in the folded four-membered ring suggests that the Ge4 ring features a certain degree of electron delocalization. Additionally, two bis(amido)-substituted germylenes (4 and 6) were isolated and structurally characterized. They exhibit analogous structural features, with each germanium center adopting a two-coordinate V-shaped configuration, the Ge–N bond lengths being very similar, and the nitrogen atoms adopting a planar triangular geometry. Notably, compound 6, bearing bulkier -N(SiiPr3)2 substituents, exhibits a significantly larger N-Ge-N bond angle (120.58°) compared to the corresponding value of 113.54° observed for compound 4 with -N(SitBuMe2)2 substituents. This clearly demonstrates that the steric bulk of the substituents exerts a remarkable influence on the molecular geometry and σ-donor ability of the lone pairs on germanium centers. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Materials (1996-1944) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.3390/ma19122516
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 12
        StartPage: 2516
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      – SubjectFull: Metal clusters
        Type: general
      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: X-ray diffraction
        Type: general
      – SubjectFull: Molecular structure
        Type: general
      – SubjectFull: Germylenes
        Type: general
      – SubjectFull: Electron delocalization
        Type: general
    Titles:
      – TitleFull: Synthesis and Characterization of a Metalloid Ge 6 Cluster with Bulky Amide Ligands.
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            NameFull: Liu, Xiaoting
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            NameFull: Zhang, Bin
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            – D: 15
              M: 06
              Text: Jun2026
              Type: published
              Y: 2026
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              Value: 19
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